CN110492068A - Redox graphene-selenium nanowires hydrogel composite material and the preparation method and application thereof - Google Patents
Redox graphene-selenium nanowires hydrogel composite material and the preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Redox graphene-selenium nanowires hydrogel composite material and the preparation method and application thereof, the composite material includes redox graphene and selenium nanowires, application the invention also includes the redox graphene-selenium nanowires hydrogel composite material preparation method and its in the battery.The preparation method of subject hydrogel composite material is easy to operate, preparation cost is low, it is suitable for industrialized production, the redox graphene-selenium nanowires hydrogel composite material can be used directly to as lithium ion battery self-supporting positive electrode, conductivity is high, volume expansion is small, large specific surface area, and it is used to prepare lithium selenium cell using the material as lithium selenium cell positive electrode, show good cycle performance and capacity retention ratio.
Description
Technical field
The present invention relates to a kind of lithium selenium cell composite positive poles and the preparation method and application thereof, and in particular to a kind of lithium selenium
Cell positive material redox graphene-selenium nanowires hydrogel composite material and the preparation method and application thereof.
Background technique
Congeners of the selenium as sulphur has the embedding Li Tuoli mechanism similar with sulphur, and selenium has and sulphur is close
Volume and capacity ratio (sulphur: 3467 mAh cm-3;Selenium: 3240 mAh cm-3).Selenium is semiconductor material simultaneously, and conductivity is remote
Much higher than the conductivity of sulphur, it is more advantageous to the utilization rate for improving lithium selenium cell active material in this way, promotes the reaction of lithium selenium cell
Activity, to effectively promote the chemical property of lithium selenium cell.
But lithium selenium cell there is a problem of similar with lithium-sulfur cell, such as blocky selenium cannot fully achieve very high utilization
The dissolution and shuttle problem of rate and more plasma seleniums, be not in specific capacity and electrochemically stable performance it is especially good, delayed lithium selenium
The practical application of battery.
CN104201349A discloses a kind of preparation method of selenium carbon electrode material with porous structure, and this method is by carbon
Material is introduced into selenium positive electrode, but it is swollen simultaneously to solve volume of the selenium positive electrode in charge and discharge process to the full extent
Swollen problem.
CN109346684A discloses a kind of carbon nanotube confinement selenium composite positive pole and preparation method thereof, the carbon nanometer
The confinement of elemental selenium nano particle is in the nano-space of the one-dimensional confinement of carbon nanotube in pipe confinement selenium composite positive pole, still,
The composite positive pole by the performance for the selenium active material that cannot completely volatilize after in selenium nano particle confinement to carbon nanotube, and
Volume expansion problem of the material caused by charge and discharge process is not can solve.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortage of prior art, provide that a kind of conductivity is high, volume expansion
Small, large specific surface area, cycle performance of battery are stablized, redox graphene-selenium nanowires hydrogel composite material.
The invention solves the second technical problem be to provide that a kind of operating method is simple, the relatively low oxygen reduction of cost
Graphite alkene-selenium nanowires hydrogel material preparation method.
The invention solves third technical problem be to provide a kind of redox graphene-selenium nanowires water-setting
The application of glue material in the battery.
The technical solution adopted by the present invention to solve the technical problems is a kind of redox graphene-selenium nanowires water
Gel rubber material, including redox graphene and selenium nanowires, the redox graphene are shape after graphene oxide reduction
At stratiform redox graphene, it is preferable that the diameter of the selenium nanowires be 5 ~ 30 nm.
The present invention solves its second technical problem the technical scheme adopted is that a kind of redox graphene-selenium nanometer
The preparation method of line hydrogel material, comprising the following steps:
(1) selenium source is added in the solution containing surfactant, stirs, obtains uniform mixed solution；
(2) mixed solution obtained by step (1) is added to containing in reducing agent solution, reduction reaction occurs for stirring, then from
The heart, washing, dispersion, drying obtain rufous selenium nanowires powder；
(3) the resulting rufous selenium nanowires powder of step (2) is added in ethanol solution, graphene oxide is then added, surpassed
Sound dispersion, obtains uniform suspension；
(4) suspension obtained by step (3) being placed in pyroreaction kettle, is sealed, reduction reaction occurs for heating, and it is cooling, it obtains
Reaction product；
(5) deionized water of reaction product obtained by step (4) is impregnated, cleaning, is then freeze-dried,.
Preferably, in step (1), the selenium source is one or more of selenium dioxide, selenium trioxide or sodium selenite.
Preferably, in step (1), the surfactant is beta-cyclodextrin, cetrimonium bromide (CTAB) or detergent alkylate
One or more of sodium sulfonate (SDBS).
Preferably, in step (1), the mass ratio of the selenium source and surfactant is 1:1 ~ 2；If the surfactant
Dosage it is too small, cannot be played a role completely on selenium source surface, if the dosage of the surfactant is excessive, will affect solution
Concentration so that subsequent reactions are difficult to control, and causes to waste.
Preferably, in step (1), the selenium source is added in the solution containing surfactant, and mixing time is 0.5 ~ 1
H, mixing speed are 300~500 r/min.
Preferably, in step (2), the reducing agent is one or more of ascorbic acid, hydroxylamine hydrochloride or hydrazine hydrate.
Preferably, in step (2), the concentration containing the reducing agent in reducing agent solution is 0.01 ~ 0.05mol/L
(more preferable 0.02 ~ 0.03mol/L).If the concentration of the reducing agent is excessive, what it is due to selection is strong reductant, can be caused into one
The generation of step side reaction and cause the waste of reducing agent, if the concentration of the reducing agent is too small, in the solution cannot completely by
Selenium source reduction.
Preferably, in step (2), the volume ratio of the mixed solution and the solution containing reducing agent is 1:1~2.
Preferably, in step (2), the time of the stirring is 4 ~ 6 h；If the time is too short, what reduction reaction carried out
Not enough thoroughly, if the overlong time, it will affect the pattern of required selenium nanowires.
Preferably, in step (2), the mode of the washing is to be taken up in order of priority with deionized water and dehydrated alcohol and alternately washed
It washs, washing times >=3 time.
Preferably, in step (2), the temperature of the drying is 60~100 DEG C, and the dry time is 24~40h.
Preferably, in step (3), the graphene oxide concentration is 1 ~ 6 mg/mL；The selenium nanowires and graphite oxide
The mass ratio of alkene is 100:3 ~ 12.If the ratio is excessive, the graphene oxide content of addition is relatively small, in later period hydrogel
It is difficult to form stable self-supporting material in forming process；If the ratio is too small, the graphene oxide content of addition is relatively
Greatly, composite material cannot protrude the performance of active material selenium.
Preferably, in step (3), the frequency of sound wave of the ultrasonic disperse is 1.5~2.5 kHz, and the ultrasonic disperse time is
0.5~1 h.If the ultrasonic disperse time is too short, selenium nanowires disperse unevenly, to easily cause material between graphene layer
Reunite；If the jitter time is too long, it is easily damaged nano-material.
Preferably, in step (4), the temperature of the heating is 150~200 DEG C.If the temperature is too low, ethanol solution
Graphene oxide cannot be restored, composite material cannot show excellent chemical property.If the temperature is excessively high, reduction is anti-
It can should cause the structure collapses for the self-supporting hydrogel material to be formed in the process.
Preferably, in step (4), the time of the heating is 10~24 h.
Preferably, described to be cooled to natural cooling in step (4).
Preferably, in step (5), wash number >=3 time after being impregnated in the deionized water.
Preferably, in step (5), the vacuum degree of the freeze-drying is 80 ~ 150 Pa, and temperature is -40 ~ -50 DEG C,
The drying time is 24~40 h.
Technical principle of the invention is: by the high price compound containing selenium while surfactant is added, with strong
Reducing agent restores to obtain selenium nanowires material；Selenium nanowires and graphene oxide are mixed again, seals and occurs in ethanol solution
High temperature reduction reaction, obtains redox graphene-selenium nanowires hydrogel composite material.This kind of selenium nanowires and reduction-oxidation
The self-supporting composite material that graphene is constituted can effectively improve the utilization rate of active material, improve chemical property.
Compared with prior art, the present invention it has the advantages that (1) redox graphene-selenium of the present invention is received
Rice noodles hydrogel composite material, selenium nanowires are fixed between redox graphene layer in the form of bracket, are formed from branch
Composite material is supportted, the utilization rate of active material can be effectively improved, enhance its electrochemical lithium storage performance, to be effectively improved electric discharge ratio
Capacity and cycle performance provide new thinking for the exploitation and research of novel high-performance electrode material；(2) also with the present invention
Former graphene oxide-selenium nanowires hydrogel composite material is assembled into battery, is 0.8~3.0 V in charging/discharging voltage, 0.1C's
Under multiplying power, the first discharge specific capacity of institute's assembled battery reaches 558.6mAh/g, and initial charge specific capacity reaches 538.5mAh/g, for the first time
Efficiency is up to 96.4%；First discharge specific capacity under the multiplying power of 1C is 366.2 mAh/g, charge specific capacity 359.9mAh/g, head
Secondary efficiency is 98.28%, and after being recycled to 250 circles, specific discharge capacity remains at 227.6 mAh/g, and charge specific capacity is
226.6mAh/g, coulombic efficiency 99.56% illustrate that material of the present invention is able to maintain the stabilization of structure, body in charge and discharge process
Product expands small, good conductivity, makes discharge and recharge reaction high reversible；(3) material preparation method of the present invention is easy, process flow letter
Short, required raw material are few at type, are suitable for industrialized production.
Detailed description of the invention
Fig. 1 is the XRD diagram of 1 hydrogel composite material of the embodiment of the present invention；
Fig. 2 is the SEM figure of 1 selenium nanowires of the embodiment of the present invention；
Fig. 3 is the SEM figure of 1 hydrogel composite material of the embodiment of the present invention；
Fig. 4 is 4 hydrogel composite material shape appearance figure of the embodiment of the present invention；
Fig. 5 is the first charge-discharge curve graph of the battery assembled with 4 hydrogel composite material of the embodiment of the present invention；
Fig. 6 is that the circulating battery 250 that 4 hydrogel composite material of the embodiment of the present invention is assembled encloses specific discharge capacity figure；
Fig. 7 is the curve of double curvature figure for the battery that 4 hydrogel composite material of the embodiment of the present invention is assembled；
Fig. 8 is the first charge-discharge curve graph for the battery that 5 hydrogel composite material of the embodiment of the present invention is assembled；
Fig. 9 is the first charge-discharge curve graph for the battery that 6 hydrogel composite material of the embodiment of the present invention is assembled；
Figure 10 is 1000 circle charge and discharge cycles curve graphs of the battery that 6 hydrogel composite material of the embodiment of the present invention is assembled.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described, but protection scope of the present invention be not limited to
Lower embodiment.
Graphene used in the embodiment of the present invention is purchased from Sigma-Aldrich, other used raw materials or chemistry
Reagent is obtained by routine business approach unless otherwise specified.
Embodiment 1
(1) it weighs 0.25 g beta-cyclodextrin to be dissolved in 50 mL deionized waters, stirs 0.5 h, after being uniformly dissolved, be added 0.25
G selenium dioxide continues to stir 0.5 h, obtains uniform mixed solution；Then it is mixed solution and pours into 50 mL rapidly
In the ascorbic acid solution of 0.028 mol/L, 5 h are stirred, solution becomes brick-red from white；After the reaction was completed, to the solution
Centrifugation after alternately being washed three times respectively with deionized water and ethyl alcohol, is placed in 80 DEG C of baking ovens 24 hours and dries, obtain rufous selenium and receive
Rice noodles；
(2) graphene oxide solution for weighing the resulting 1 g selenium nanowires of step (1), 10 mL, 3 mg/mL, pours into 30 mL
In ethanol solution, ultrasonic disperse 30min obtains uniform suspension；
(3) suspension obtained by step (2) is poured into 100 mL polytetrafluoroethylene (PTFE) pyroreaction kettles, steel shell sealing is placed in air blast
In baking oven, 180 DEG C are heated to, reacts 12 h, natural cooling obtains black hydrogel composite material；
(4) the resulting black hydrogel composite material of step (3) is placed in clear water and is impregnated, after washing three times, place it in-
24 h are freeze-dried at 45 DEG C,.
Shown in Fig. 1, redox graphene-selenium nanowires hydrogel composite material XRD diagram obtained by the present embodiment is contained only
There are selenium, carbon, without other impurity.
Shown in Fig. 2, selenium nanowires SEM shape appearance figure obtained by the present embodiment, selenium nanowires are evenly distributed, soilless sticking phenomenon, should
The diameter of selenium nanowires is 5 ~ 30 nm.
Shown in Fig. 3, the present embodiment redox graphene-selenium nanowires hydrogel composite material SEM figure, reduction-oxidation
Graphene dispersion is uniform, forms self-supporting material by skeleton of selenium nanowires.
Embodiment 2
(1) 0.25 g CTAB is weighed in 50 mL deionized waters, stirs 0.5 h, and after being uniformly dissolved, 0.25 g is added to it
Selenium dioxide continues to stir 0.5 h, obtains uniform mixed solution.Then it is mixed solution and pours into 50 mL 0.028 rapidly
In the ascorbic acid solution of mol/L, 5 h are stirred, solution becomes brick-red from white.After the reaction was completed, which is centrifuged, is used
After deionized water and ethyl alcohol alternately wash three times respectively, it is placed in 80 DEG C of baking ovens 24 hours and dries, obtain rufous selenium nanowires.
(2) the resulting 0.5 g selenium nanowires of step (1), 10 mL, 3 mg/mL graphene oxide solution are weighed, pour into 30
In mL ethanol solution, 30 min of ultrasonic disperse obtains uniform suspension.
(3) suspension obtained by step (2) is poured into 100 mL polytetrafluoroethylene (PTFE) pyroreaction kettles, steel shell sealing is placed in
In convection oven, 180 DEG C are heated to, reacts 12 h, natural cooling obtains black hydrogel composite material.
(4) the resulting black hydrogel composite material of step (3) is placed in clear water and is impregnated, and after washing three times repeatedly,
It places it at -45 DEG C and is freeze-dried, dry 24 h obtain redox graphene-selenium nanowires hydrogel composite material.
Through detecting, redox graphene-selenium nanowires hydrogel composite material XRD diagram obtained by the present embodiment is contained only
There are selenium, carbon, without other impurity.
Through detecting, selenium nanowires SEM shape appearance figure obtained by the present embodiment, selenium nanowires are evenly distributed, soilless sticking phenomenon, the selenium
The diameter of nano wire is 5 ~ 30 nm.Gained redox graphene-selenium nanowires hydrogel composite material SEM figure, oxygen reduction
Graphite alkene is uniformly dispersed, and forms self-supporting material by skeleton of selenium nanowires.
Embodiment 3
(1) it weighs 0.25 g beta-cyclodextrin to be dissolved in 50 mL deionized waters, stirs 0.5 h, after being uniformly dissolved, be added to it
0.25 g selenium dioxide continues to stir 0.5 h, obtains uniform mixed solution.Then it is mixed solution and pours into 50 rapidly
In the ascorbic acid solution of mL 0.028M, 5 h are stirred, solution becomes brick-red from white.After the reaction was completed, to the solution from
The heart after alternately being washed three times respectively with deionized water and ethyl alcohol, is placed in 80 DEG C of baking ovens 24 hours and dries, obtain rufous selenium nanometer
Line.
(2) graphene oxide solution of the resulting 0.5 g selenium nanowires of step (1), 20 mL, 3 mg/mL are weighed,
Enter in 30 mL ethanol solutions, 30 min of ultrasonic disperse obtains uniform suspension.
(3) suspension obtained by step (2) is poured into 100 mL polytetrafluoroethylene (PTFE) pyroreaction kettles, steel shell sealing is placed in
In convection oven, 180 DEG C are heated to, reacts 12 h, natural cooling obtains black hydrogel composite material.
(4) the resulting black hydrogel composite material of step (3) is placed in clear water and is impregnated, and after washing three times repeatedly,
It places it at -45 DEG C and is freeze-dried 24 h, obtain redox graphene-selenium nanowires hydrogel composite material.
Through detecting, redox graphene-selenium nanowires hydrogel composite material XRD diagram obtained by the present embodiment is contained only
There are selenium, carbon, without other impurity.
Through detecting, selenium nanowires SEM shape appearance figure obtained by the present embodiment, selenium nanowires are evenly distributed, soilless sticking phenomenon, the selenium
The diameter of nano wire is 5 ~ 30 nm.Gained redox graphene-selenium nanowires hydrogel composite material SEM figure, oxygen reduction
Graphite alkene is uniformly dispersed, and forms self-supporting material by skeleton of selenium nanowires.
Embodiment 4
(1) preparation of subject hydrogel material: with embodiment 1.
(2) assembling of battery: by redox graphene-selenium nanowires hydrogel composite material knife obtained by the present embodiment
Piece is thinly sliced, and is placed on roll squeezer and is densified to suitable diaphragm density, and the electrode slice after pressure is punched into circle using slicer
Shape electrode slice, and weigh quality.
(3) performance measurement: above-mentioned the electrode obtained piece, electrode shell and diaphragm are moved into the glove box full of argon gas, diaphragm
Porous C elgard2400 is selected, (solvent is ethylene carbonate EC, carbonic acid to electrolyte standard 1mol/L LiPF6 solution
The solution of dimethyl ester DMC, diethyl carbonate DEC 1:1:1 mixing by volume), it is assembled into the button cell of CR2025, is carried out
Charge-discharge test.
Fig. 4 is the present embodiment redox graphene-selenium nanowires hydrogel composite material, and cylindrical, matter is soft, can be used
Blade is thinly sliced to be placed on roll squeezer and is compacted, then the electrode slice after pressure is punched into circular electrode slice with slicer.
By Fig. 5,6,7 it is found that the electricity that the present embodiment redox graphene-selenium nanowires hydrogel composite material is assembled
Pond is 0.8~3.0 V in charging/discharging voltage, and under the multiplying power of 0.1C, the first discharge specific capacity of institute's assembled battery is up to 558.6
MAh/g, initial charge specific capacity is up to 538.5 mAh/g, first charge discharge efficiency 96.4%；First discharge specific capacity under the multiplying power of 1C
Up to 366.2 mAh/g, charge specific capacity 359.9mAh/g, first charge discharge efficiency 98.28%；After being recycled to 250 circles, discharge specific volume
Amount still reaches 227.6mAh/g, and charge specific capacity illustrates composite material of the present invention up to 226.6 mAh/g, coulombic efficiency 99.56%
The stabilization of structure is able to maintain in charge and discharge process, volume expansion is small, good conductivity, makes discharge and recharge reaction high reversible.
Embodiment 5
(1) preparation of subject hydrogel material: with embodiment 2.
(2) assembling of battery: with embodiment 4.
(3) measurement of performance: through detecting, the present embodiment redox graphene-selenium nanowires hydrogel composite material institute
The battery of assembling is 0.8~3.0 V in charging/discharging voltage, and under the multiplying power of 0.1C, the first discharge specific capacity of institute's assembled battery reaches
540.8mAh/g, charge specific capacity reach 522.2mAh/g, first charge discharge efficiency 96.56%, specific capacity connects under the current density
Nearly theoretical capacity.
Embodiment 6
(1) preparation of subject hydrogel material: with embodiment 3.
(2) assembling of battery: with embodiment 4.
(3) measurement of performance: through detecting, the present embodiment redox graphene-selenium nanowires hydrogel composite material institute
The battery of assembling is 0.8~3.0 V in charging/discharging voltage, and under the multiplying power of 0.1C, the first discharge specific capacity of institute's assembled battery reaches
526.3mAh/g, charge specific capacity reach 507.9mAh/g, first charge discharge efficiency 96.5%；After 1000 circle of circulation, specific discharge capacity reaches
202.8mAh/g, charge specific capacity are 196.9 mAh/g, and coulombic efficiency 97.1% illustrates the charge and discharge of composite material of the present invention
Performance is stablized, and cycle performance is excellent.
Claims (10)
1. a kind of redox graphene-selenium nanowires hydrogel composite material, which is characterized in that by redox graphene and
Selenium nanowires are constituted, and the redox graphene is stratiform redox graphene.
2. redox graphene-selenium nanowires hydrogel composite material according to claim 1, which is characterized in that described
The diameter of selenium nanowires is 5 ~ 30 nm.
3. a kind of preparation method of redox graphene as claimed in claim 1 or 2-selenium nanowires hydrogel composite material,
It is characterized in that, comprising the following steps:
(1) selenium source is added in the solution containing surfactant, stirs, obtains uniform mixed solution；
(2) mixed solution obtained by step (1) is added in the solution containing reducing agent, is stirred, reduction reaction occurs, then
Centrifugation, washing, dispersion, drying, obtain rufous selenium nanowires powder；
(3) the resulting rufous selenium nanowires powder of step (2) is added in ethanol solution, graphene oxide is then added, surpassed
Sound dispersion, obtains uniform suspension；
(4) suspension obtained by step (3) being placed in pyroreaction kettle, is sealed, reduction reaction occurs for heating, and it is cooling, it obtains
Reaction product；
(5) deionized water of reaction product obtained by step (4) is impregnated, cleaning, is then freeze-dried.
4. redox graphene described according to claim 1 ~ one of 3-selenium nanowires hydrogel composite material preparation method,
It is characterized by: the selenium source is one or several in selenium dioxide, selenium trioxide or sodium selenite in step (1)；The table
Face activating agent is beta-cyclodextrin, and one or more of cetrimonium bromide (CTAB) or neopelex (SDBS) are described
The mass ratio of selenium source and surfactant is 1:1 ~ 2.
5. redox graphene described according to claim 1 ~ one of 4-selenium nanowires hydrogel composite material preparation method,
It is characterized by: the time of the stirring is 0.5 ~ 1 h in step (1), the speed of stirring is 300~500 r/min.
6. redox graphene described according to claim 1 ~ one of 5-selenium nanowires hydrogel composite material preparation method,
It is characterized by: reducing agent described in step (2) is one or more of ascorbic acid, hydroxylamine hydrochloride or hydrazine hydrate, it is described
The concentration of reducing agent is 0.01 ~ 0.05mol/L, and more preferable 0.02 ~ 0.03mol/L, the time of the stirring is 4 ~ 6 h；Institute
The mode for stating washing is to be taken up in order of priority alternately to wash with deionized water and dehydrated alcohol, number >=3 time of the washing；It is described dry
Dry temperature is 60~100 DEG C, and drying time is 24~40h.
7. redox graphene described according to claim 1 ~ one of 6-selenium nanowires hydrogel composite material preparation method,
It is characterized by: the graphene oxide concentration is 1 ~ 6 mg/mL in step (3)；The selenium nanowires and graphene oxide
Mass ratio is 100:3 ~ 12；The frequency of sound wave of the ultrasonic disperse is 1.5~2.5kHz, and the time of ultrasonic disperse is 0.5 ~ 1 h.
8. redox graphene described according to claim 1 ~ one of 7-selenium nanowires hydrogel composite material preparation method,
It is characterized by: the temperature of the heating is 150~200 DEG C in step (4), the time of the heating is 10~24 h.
9. redox graphene described according to claim 1 ~ one of 8-selenium nanowires hydrogel composite material preparation method,
It is characterized by: in step (5), the vacuum degree < 100Pa of the freeze-drying, < -40 DEG C of temperature, the time of the drying is
24~40 h.
10. redox graphene-the application of selenium nanowires hydrogel composite material in the battery according to claim 1.
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| CN111446441A (en) * | 2020-04-03 | 2020-07-24 | 浙江工业大学 | Nano-selenium-reduced graphene oxide composite material and preparation and application thereof |
| CN112499599A (en) * | 2020-11-30 | 2021-03-16 | 北京化工大学 | Macroscopic preparation method of ultra-long Se nanowire |
| CN113097484A (en) * | 2021-04-01 | 2021-07-09 | 陕西科技大学 | Carbon-coated sandwich structure SnSe/r-GO @ C compound and preparation method and application thereof |
| CN116240021A (en) * | 2022-12-23 | 2023-06-09 | 南京贝迪新材料科技股份有限公司 | Graphene/selenium nanocrystalline-based composite material, film and preparation method thereof |
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| CN116240021B (en) * | 2022-12-23 | 2023-12-19 | 南京贝迪新材料科技股份有限公司 | Graphene/selenium nanocrystalline-based composite material, film and preparation method thereof |
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